This disclosure relates to a polymer that includes a first comonomer repeat unit containing a benzothiadiazole moiety, a thiophene oxide moiety, a cyclopentadithiophene oxide moiety, a thiadiazoloquinoxaline moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, or a tetrahydroisoindole moiety. The polymer can be used as a photoactive material in a photovoltaic cell. This disclosure also relates to such photovoltaic cells, as well as modules containing such photovoltaic cells.
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1. A photovoltaic cell, comprising:
a first electrode,
a second electrode, and
a photoactive material disposed between the first and second electrodes, the photoactive material comprising a polymer,
wherein the polymer is
##STR00043##
n being an integer greater than 1.
3. A device, comprising:
a first electrode,
a second electrode, and
a photoactive material disposed between the first and second electrodes, the photoactive material comprising a polymer including first and second monomer repeat units, the first monomer repeat unit comprising a benzothiadiazole moiety of formula (II):
##STR00046##
and a second monomer repeat unit comprising a cyclopentadithiophene moiety of formula (I):
##STR00047##
wherein each of R1, R2, R3, R4, R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R, in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
2. A photovoltaic cell, comprising:
a first electrode,
a second electrode, and
a photoactive material disposed between the first and second electrodes, the photoactive material comprising a polymer including first and second monomer repeat units, the first monomer repeat unit comprising a benzothiadiazole moiety of formula (II):
##STR00044##
and the second monomer repeat unit comprising a cyclopentadithiophene moiety of formula (I):
##STR00045##
wherein each of R1, R2, R3, R4, R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R, in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
4. A device, comprising:
a first electrode,
a second electrode, and
a photoactive material disposed between the first and second electrodes, the photoactive material comprising a polymer including a first monomer repeat unit and a second monomer repeat unit different from the first monomer repeat unit, the first monomer repeat unit comprising a cyclopentadithiophene moiety of formula (I):
##STR00048##
and the second monomer repeat unit comprising a thiadiazoloquinoxaline moiety of formula (III), a benzoisothiazole moiety of formula (VI), a benzothiazole moiety of formula (VII), a thienothiophene moiety of formula (XI), a dithienothiophene moiety of formula (XIII), or a tetrahydroisoindole moiety of formula (XVI):
##STR00049##
wherein
each of X and Y, independently, is CH2, O, or S;
each of R1, R2, R3, R4, R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R, in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; and
R7 is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
5. The device of
6. The device of
7. The device of
8. The device of
9. The device of
10. The device of
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This application is a continuation-in-part of U.S. Utility Application Ser. No. 11/450,521, filed Jun. 9, 2006 now U.S. Pat. No. 7,781,673, which in turn is a continuation-in-part of U.S. Utility Application Ser. No. 11/375,643, filed Mar. 14, 2006 now U.S. Pat. No. 7,772,485, which claims priority to U.S. Provisional Application Ser. No. 60/699,123, filed Jul. 14, 2005, the contents of which are hereby incorporated by reference.
This invention was supported by contract number W911QY-04-C-0070 awarded by the Defense Advanced Research Projects Agency. The U.S. Government has certain rights in the invention.
This disclosure generally relates to the field of electron donor materials, as well as related photovoltaic cells.
Photovoltaic cells are commonly used to transfer energy in the form of light into energy in the form of electricity. A typical photovoltaic cell includes a photoactive material disposed between two electrodes. Generally, light passes through one or both of the electrodes to interact with the photoactive material. As a result, the ability of one or both of the electrodes to transmit light (e.g., light at one or more wavelengths absorbed by a photoactive material) can limit the overall efficiency of a photovoltaic cell. In many photovoltaic cells, a film of semiconductive material (e.g., indium tin oxide) is used to form the electrode(s) through which light passes because, although the semiconductive material can have a lower electrical conductivity than electrically conductive materials, the semiconductive material can transmit more light than many electrically conductive materials.
An aspect of the invention relates to a new combination of monomers that produce polymers, wherein the polymers have properties suitable for use as charge carriers in the active layer of a photovoltaic cell.
In one aspect, the invention features a class of co-polymers including at least two co-monomers, at least one of which is a cyclopentadithiophene.
In another aspect, this invention features a photovoltaic cell including a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first comonomer repeat unit and a second comonomer repeat unit. The first comonomer repeat unit includes a cyclopentadithiophene moiety. The second comonomer repeat unit includes a silole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, or a tetrahydroisoindole moiety.
In another aspect, this invention features a photovoltaic cell including a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first comonomer repeat unit and a second comonomer repeat unit different from the first comonomer repeat unit. The first comonomer repeat unit includes a cyclopentadithiophene moiety.
In another aspect, this invention features a polymer that includes a first comonomer repeat unit containing a cyclopentadithiophene moiety, and a second comonomer repeat unit containing a benzothiadiazole moiety, a thiadiazoloquinoxaline moiety, a cyclopentadithiophene oxide moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thiophene oxide moiety, a fluorene moiety, a thiophene moiety, a silole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, a tetrahydroisoindole moiety, or a moiety containing at least three thiophene moieties.
In another aspect, this invention features a polymer that includes a first comonomer repeat unit and a second comonomer repeat unit different from the first comonomer repeat unit. The first comonomer repeat unit contains a cyclopentadithiophene moiety substituted with at least one substituent selected from the group consisting of hexyl, ethylhexyl, dimethyloctyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, and C3-C20 heterocycloalkyl.
In another aspect, this invention features a device (e.g., a photovoltaic cell) that includes a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first monomer repeat unit, which includes a benzothiadiazole moiety, a thiophene oxide moiety, a cyclopentadithiophene oxide moiety, a thiadiazoloquinoxaline moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, a tetrahydroisoindole moiety, a fluorene moiety, a thiophene moiety, a silole moiety, or a fluorene moiety.
In another aspect, this invention features a device (e.g., a photovoltaic cell) that includes a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first monomer repeat unit, which includes a cyclopentadithiophene moiety substituted with at least one substituent selected from the group consisting of hexyl, ethylhexyl, dimethyloctyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl halo, CN, NO2, or SO2R, in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
Embodiments can include one or more of the following features.
In some embodiments, the cyclopentadithiophene moiety is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. Examples of C1-C20 alkyl can be hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl.
In some embodiments, the cyclopentadithiophene moiety can be substituted at 4-position.
In some embodiments, the first monomer or comonomer repeat unit can include a cyclopentadithiophene moiety of formula (I):
##STR00001##
In formula (I), each of R1, R2, R3, and R4, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R1 and R2, independently, is hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl. In certain embodiments, each of R1 and R2, independently, is hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl. In some embodiments, one of R1 and R2 is hexyl, ethylhexyl, dimethyloctyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl, the other of R1 and R2 is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R1 and R2, independently, is C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3). In certain embodiments, each of R1 and R2, independently, is C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo.
In some embodiments, the second comonomer repeat unit can include a benzothiadiazole moiety, a thiadiazoloquinoxaline moiety, a cyclopentadithiophene oxide moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thiophene oxide moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, a tetrahydroisoindole moiety, a fluorene moiety, a thiophene moiety, or a silole moiety, each of which is optionally substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, the second comonomer repeat unit can include a 3,4-benzo-1,2,5-thiadiazole moiety.
In some embodiments, the second comonomer repeat unit can include a benzothiadiazole moiety of formula (II), a thiadiazoloquinoxaline moiety of formula (III), a cyclopentadithiophene dioxide moiety of formula (IV), a cyclopentadithiophene monoxide moiety of formula (V), a benzoisothiazole moiety of formula (VI), a benzothiazole moiety of formula (VII), a thiophene dioxide moiety of formula (VIII), a cyclopentadithiophene dioxide moiety of formula (IX), or a cyclopentadithiophene tetraoxide moiety of formula (X):
##STR00002##
##STR00003##
in which each of R5, R6, and R7, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, the second comonomer repeat unit can include a benzothiadiazole moiety of formula (II). In certain embodiments, R5 and R6 is H.
In some embodiments, the second comonomer repeat unit can include at least three thiophene moieties. In some embodiments, at least one of the thiophene moieties is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In certain embodiments, the second comonomer repeat unit includes five thiophene moieties.
In some embodiments, the second comonomer repeat unit can include a thienothiophene moiety of formula (XI), a thienothiophene tetraoxide moiety of formula (XII), a dithienothiophene moiety of formula (XIII), a dithienothiophene dioxide moiety of formula (XIV), a dithienothiophene tetraoxide moiety of formula (XV), a tetrahydroisoindole moiety of formula (XVI), a thienothiophene dioxide moiety of formula (XVII), or a dithienothiophene dioxide moiety of formula (XVIII):
##STR00004##
in which each of X and Y, independently, is CH2, O, or S; each of R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R, in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; and R7 is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
In some embodiments, the polymer can further include a third comonomer repeat unit that contains a thiophene moiety or a fluorene moiety. In some embodiments, the thiophene or fluorene moiety is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, and C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
In some embodiments, the first monomer or comonomer repeat unit can include a benzothiadiazole moiety of formula (II), a thiophene dioxide moiety of formula (VIII), a cyclopentadithiophene tetraoxide moiety of formula (X), or a fluorene moiety of formula (XIX):
##STR00005##
in which each of R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R. R can be C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R5 and R6 can be C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3).
In some embodiments, the polymer can include a second monomer repeat unit different from the first monomer repeat unit. The second monomer repeat unit can include a cyclopentadithiophene moiety, a benzothiadiazole moiety, a thiophene oxide moiety, a cyclopentadithiophene oxide moiety, a fluorene moiety, or a thiophene moiety.
In some embodiments, the first or second monomer repeat unit can include at least one substituent on a ring selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. The substituent can be hexyl, ethylhexyl, or C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3).
In some embodiments, the second monomer repeat unit can include a cyclopentadithiophene moiety of formula (I), a benzothiadiazole moiety of formula (II), a thiophene dioxide moiety of formula (VIII), a cyclopentadithiophene tetraoxide moiety of formula (X), a fluorene moiety of formula (XIX), a thiophene moiety of formula (XX), or a silole moiety of formula (XXI):
##STR00006##
in which each of R1, R2, R3, R4, R5, R6, R7, and R8, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R. R can be C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R1, R2, R3, R4, R5, R6, R7, and R8, can be C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3).
In some embodiments, when the second comonomer contains a silole moiety of formula (XXI), at least one of R5, R6, R7 and R8 can be C1-C20 alkyl optionally substituted with halo, or aryl optionally substituted with C1-C20 alkyl. In certain embodiments, each of R5 and R6, independently can be aryl optionally substituted with C1-C20 alkyl, and each of R7 and R8, independently, can be C1-C20 alkyl optionally substituted with halo. An example of a silole moiety is
##STR00007##
In some embodiments, the polymer can be an electron donor material or an electron acceptor material.
In some embodiments, the polymer can be
##STR00008##
in which n can be an integer greater than 1.
In some embodiments, the photovoltaic cell can be a tandem photovoltaic cell.
In some embodiments, the photoactive material can include an electron acceptor material. In some embodiments, the electron acceptor material can be a fullerene (e.g., C61-phenyl-butyric acid methyl ester, PCBM).
In some embodiments, the polymer and the electron acceptor material each can have a LUMO energy level. The LUMO energy level of the polymer can be at least about 0.2 eV (e.g., at least about 0.3 eV) less negative than the LUMO energy level of the electron acceptor material.
In some embodiments, the device can be an organic semiconductive device. In certain embodiments, the device can be a member selected from the group consisting of field effect transistors, photodetectors, photovoltaic detectors, imaging devices, light emitting diodes, lasing devices, conversion layers, amplifiers and emitters, storage elements, and electrochromic devices.
Embodiments can provide one or more of the following advantages.
In some embodiments, using a polymer containing a cyclopentadithiophene moiety can be advantageous because the cyclopentadithiophene moiety can contribute to a shift in the maximum absorption wavelength toward the red or near IR region of the electromagnetic spectrum. When such a polymer is incorporated into a photovoltaic cell, the current and efficiency of the cell can increase.
In some embodiments, substituted fullerenes or polymers containing substituted monomer repeat units (e.g., substituted with long-chain alkoxy groups such as oligomeric ethylene oxides or fluorinated alkoxy groups) can have improved solubility in organic solvents and can form an photoactive layer with improved morphology.
In some embodiments, a polymer containing a silole moiety can absorb light at a relatively long wavelength and have improved solubility in organic solvents. In some embodiments, a polymer containing a silole moiety can be used to prepare an electron donor material with improved semiconductive properties.
In some embodiments, a polymer fullerene cell containing a polymer described above can have a band gap that is relatively ideal for its intended purposes.
In some embodiments, a photovoltaic cell having high cell voltage can be created, whereby the HOMO level of the polymer is at least about 0.2 electron volts more negative relative to the LUMO or conduction band of an electron acceptor material.
In some embodiments, a photovoltaic cell containing a polymer described above can have relatively fast and efficient transfer of an electron to an electron acceptor material, whereby the LUMO of the donor is at least about 0.2 electron volt (e.g., at least about 0.3 electron volt) less negative than the conduction band of the electron acceptor material.
In some embodiments, a photovoltaic cell containing a polymer described above can have relatively fast charge separation, whereby the charge mobility of the positive charge, or hole, is relatively high and falls within the range of 10−4 to 10−1 cm2/Vs.
In some embodiments, the polymer is soluble in an organic solvent and/or film forming.
In some embodiments, the polymer is optically non-scattering.
In some embodiments, the polymer can be used in organic field effect transistors and OLEDs.
Other features and advantages of the invention will be apparent from the description, drawings, and claims.
Like reference symbols in the various drawings indicate like elements.
In general, during use, light impinges on the surface of substrate 110, and passes through substrate 110, cathode 120, and hole carrier layer 130. The light then interacts with active layer 140, causing electrons to be transferred from the electron donor material (e.g., a polymer described above) to the electron acceptor material (e.g., PCBM). The electron acceptor material then transmits the electrons through hole blocking layer 150 to anode 160, and the electron donor material transfers holes through hole carrier layer 130 to cathode 120. Anode 160 and cathode 120 are in electrical connection via an external load so that electrons pass from anode 160, through the load, and to cathode 120.
Electron acceptor materials of active layer 140 can include fullerenes. In some embodiments, active layer 140 can include one or more unsubstituted fullerenes and/or one or more substituted fullerenes. Examples of unsubstituted fullerenes include C60, C70), C76, C78, C82, C84, and C92. Examples of substituted fullerenes include PCBM or fullerenes substituted with C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3). Without wishing to be bound by theory, it is believed that fullerenes substituted with long-chain alkoxy groups (e.g., oligomeric ethylene oxides) or fluorinated alkoxy groups have improved solubility in organic solvents and can form an photoactive layer with improved morphology.
In some embodiments, the electron acceptor materials can include polymers (e.g., homopolymers or copolymers). A polymers mentioned herein include at least two identical or different monomer repeat units (e.g., at least 5 monomer repeat units, at least 10 monomer repeat units, at least 50 monomer repeat units, at least 100 monomer repeat units, or at least 500 monomer repeat units). A copolymer mentioned herein refers to a polymer that includes at least two co-monomers of differing structures. In some embodiments, the polymers used as an electron acceptor material can include one or more monomer repeat units listed in Tables 1 and 2 below. Specifically, Table 1 lists examples of the monomers that can be used as an electron donating monomer and can serve as a conjugative link. Table 2 lists examples of the monomers that can be used as an electron withdrawing monomer. Note that depending on the substituents, monomers listed in Table 1 can also be used as electron withdrawing monomers and monomers listed in Table 2 can also be used as electron donating monomers. Preferably, the polymers used as an electron acceptor material include a high molar percentage (e.g., at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%) of an electron withdrawing monomer.
Electron donor materials of active layer 140 can include polymers (e.g., homopolymers or copolymers). In some embodiments, the polymers used as an electron donor material can include one or more monomer repeat units listed Tables 1 and 2. Preferably, the polymers used as an electron donor material include a high molar percentage (e.g., at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%) of an electron donating monomer. In some embodiments, the polymers include a monomer containing C1-C20 alkoxy on a ring, which is optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3). Without wishing to be bound by theory, it is believed that polymers containing monomers substituted with long-chain alkoxy groups (e.g., oligomeric ethylene oxides) or fluorinated alkoxy groups have improved solubility in organic solvents and can form an photoactive layer with improved morphology.
TABLE 1
##STR00009##
##STR00010##
##STR00011##
TABLE 2
##STR00012##
##STR00013##
##STR00014##
##STR00015##
##STR00016##
##STR00017##
##STR00018##
##STR00019##
##STR00020##
##STR00021##
##STR00022##
##STR00023##
##STR00024##
##STR00025##
##STR00026##
##STR00027##
##STR00028##
##STR00029##
Referring to formulas listed in Tables 1 and 2 above, each of X and Y, independently, can be CH2, O, or S; each of R1, R2, R3, R4, R5, R6, R7, and R8, independently, can be H, C1-C20 alkyl, C1-C20 alkoxy, aryl (e.g., phenyl or substituted phenyl), heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R; and R7 can be H, C1-C20 alkyl, C1-C20 alkoxy, aryl (e.g., phenyl or substituted phenyl), heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. An alkyl can be saturated or unsaturated and branch or straight chained. A C1-C20 alkyl contains 1 to 20 carbon atoms (e.g., one, two , three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of alkyl moieties include —CH3, —CH2—, —CH2═CH2—, —CH2—CH═CH2, and branched —C3H7. An alkoxy can be branch or straight chained and saturated or unsaturated. An C1-C20 alkoxy contains an oxygen radical and 1 to 20 carbon atoms (e.g., one, two , three, four, five, six, seven, eight, nine, 10, 11,12,13,14,15,16, 17,18, 19, and 20 carbon atoms). Examples of alkoxy moieties include —OCH3 and —OCH═C2H4. A cycloalkyl can be either saturated or unsaturated. A C3-C20 cycloalkyl contains 3 to 20 carbon atoms (e.g., three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of cycloalkyl moieities include cyclohexyl and cyclohexen-3-yl. A heterocycloalkyl can also be either saturated or unsaturated. A C3-C20 heterocycloalkyl contains at least one ring heteroatom (e.g., O, N, and S) and 3 to 20 carbon atoms (e.g., three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of heterocycloalkyl moieties include 4-tetrahydropyranyl and 4-pyranyl. An aryl can contain one or more aromatic rings. Examples of aryl moieties include phenyl, phenylene, naphthyl, naphthylene, pyrenyl, anthryl, and phenanthryl. A heteroaryl can contain one or more aromatic rings, at least one of which contains at least one ring heteroatom (e.g., O, N, and S). Examples of heteroaryl moieties include furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.
Alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl mentioned herein include both substituted and unsubstituted moieties, unless specified otherwise. Examples of substituents on cycloalkyl, heterocycloalkyl, aryl, and heteroaryl include C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, amino, C1-C10 alkylamino, C1-C20 dialkylamino, arylamino, diarylamino, hydroxyl, halogen, thio, C1-C10 alkylthio, arylthio, C1-C10 alkylsulfonyl, arylsulfonyl, cyano, nitro, acyl, acyloxy, carboxyl, and carboxylic ester. Examples of substituents on alkyl include all of the above-recited substituents except C1-C20 alkyl. Cycloalkyl, heterocycloalkyl, aryl, and heteroaryl also include fused groups.
The copolymers described above can be prepared by methods known in the art. For example, a copolymer can be prepared by a cross-coupling reaction between one or more comonomers containing two alkylstannyl groups and one or more comonomers containing two halo groups in the presence of a transition metal catalyst. As another example, a copolymer can be prepared by a cross-coupling reaction between one or more comonomers containing two borate groups and one or more comonomers containing two halo groups in the presence of a transition metal catalyst. The comonomers can be prepared by the methods described herein or by the methods know in the art, such as those described in Coppo et al., Macromolecules 2003, 36, 2705-2711 and Kurt et al., J Heterocycl. Chem. 1970, 6, 629, the contents of which are hereby incorporated by reference.
Table 3 below lists three exemplary polymers (i.e., polymers 1-3) described in the Summary section above. These polymers can have unique properties, which make them particularly suitable as charge carriers in the active layer of a photovoltaic cell. Polymers 1 and 2 can be obtained by the methods described in Examples 4 and 7 below.
TABLE 3
Polymer 1
##STR00030##
Polymer 2
##STR00031##
Polymer 3
##STR00032##
Generally, one co-monomer in the polymers described in the Summary section above is a cyclopentadithiophene. An advantage of a co-polymer containing a cyclopentadithiophene moiety is that its absorption wavelength can shift toward the red and near IR portion (e.g., 650-800 nm) of the electromagnetic spectrum, which is not accessible by most other polymers. When such a co-polymer is incorporated into a photovoltaic cell, it enables the cell to absorb the light in this region of the spectrum, thereby increasing the current and efficiency of the cell.
The polymers described above can be useful in solar power technology because the band gap is close to ideal for a photovoltaic cell (e.g., a polymer-fullerene cell). The HOMO level of the polymers can be positioned correctly relative to the LUMO of an electron acceptor (e.g., PCBM) in a photovoltaic cell (e.g., a polymer-fullerene cell), allowing for high cell voltage. The LUMO of the polymers can be positioned correctly relative to the conduction band of the electron acceptor in a photovoltaic cell, thereby creating efficient transfer of an electron to the electron acceptor. For example, using a polymer having a band gap of about 1.4-1.6 eV can significantly enhance cell voltage. Cell performance, specifically efficiency, cam benefit from both an increase in photocurrent and an increase in cell voltage, and can approach and even exceed 15% efficiency. The positive charge mobility of the polymers can be relatively high and approximately in the range of 10−4 to 10−1cm2/Vs. In general, the relatively high positive charge mobility allows for relatively fast charge separation. The polymers can also be soluble in an organic solvent and/or film forming. Further, the polymers can be optically non-scattering.
Components in photovoltaic cell other than the electro acceptor materials and he electron donor materials are known in the art, such as those described in U.S. patent application Ser. No. 10/723,554, the contents of which are incorporated herein by references.
In some embodiments, the polymer described above can be used as an electron donor material or an electro acceptor material in a system in which two photovoltaic cells share a common electrode. Such a system is also known as tandem photovoltaic cell. Examples of tandem photovoltaic cells are discussed in U.S. patent application Ser. No. 10/558,878, filed Nov. 29, 2005, the contents of which are hereby incorporated by reference.
As an example,
Each of photoactive layers 230 and 250 can contain at least one semiconductive material. In some embodiments, the semiconductive material in photoactive layer 230 has the same band gap as the semiconductive material in photoactive layer 250. In certain embodiments, the semiconductive material in photoactive layer 230 has a band gap different from that of the semiconductive material in photoactive layer 250. Without wishing to be bound by theory, it is believed that incident light not absorbed by one photoactive layer can be absorbed by the other photoactive layer, thereby maximizing the absorption of the incident light.
In some embodiments, at least one of photoactive layers 230 and 250 can contain an electron acceptor material (e.g., PCBM or a polymer described above) and an electron donor material (e.g., a polymer described above). In general, suitable electron acceptor materials and electron donor materials can be those described above. In certain embodiments, each of photoactive layers 230 and 250 contains an electron acceptor material and an electron donor material.
Substrate 210 can be formed of one or more suitable polymers, such as those described in U.S. patent application Ser. No. 10/723,554. In some embodiments, an additional substrate (not shown in
Photovoltaic cell 200 can further contain a hole carrier layer (not shown in
While photovoltaic cells have been described above, in some embodiments, the polymers described herein can be used in other devices and systems. For example, the polymers can be used in suitable organic semiconductive devices, such as field effect transistors, photodetectors (e.g., IR detectors), photovoltaic detectors, imaging devices (e.g., RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (e.g., organic LEDs or IR or near IR LEDs), lasing devices, conversion layers (e.g., layers that convert visible emission into IR emission), amplifiers and emitters for telecommunication (e.g., dopants for fibers), storage elements (e.g., holographic storage elements), and electrochromic devices (e.g., electrochromic displays).
The following examples are illustrative and not intended to be limiting.
##STR00033##
4H-Cyclopenta[2,1-b;3,4-b′]dithiophene was synthesized according to literature procedure illustrated in Coppo et al., Macromolecules 2003, 36, 2705-2711. All other starting materials were purchased from Sigma-Aldrich and used as received.
4H-Cyclopenta[2,1-b;3,4-b′]dithiophene (1.5 g, 0.00843 mol) was dissolved in DMSO (50 mL). The solution was purged with nitrogen, and grounded KOH (1.89 g, 0.0337 mol) and sodium iodide (50 mg) were added, followed by hexyl bromide (3.02 g, 0.0169 mol). The reaction was stirred for 17 h under nitrogen at room temperature. Water was added and the reaction was extracted with t-butyl-methyl ether. The organic layer was separated and dried over magnesium sulfate. Solvent was removed under vacuum and the residue was purified by chromatography using hexanes as eluent. Fractions containing pure 4,4-dixeyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene product were combined and the solvents evaporated. The product was obtained as a colorless oil. Yield: 2.36 g (81%).
##STR00034##
Starting material 4,4-dihexyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (1.5 g, 0.00433 mol) was dissolved in dry THF (30 mL). The solution was cooled to −78° C. and butyl lithium (6.1 mL, 0.0130 mol) was added drop wise. The reaction was stirred at this temperature for 2 h and warmed to room temperature, stirred for 3 h. Again reaction was cooled to −78° C. and trimethyltin chloride (1 M in hexanes, 16.0 mL, 16.0 mmol) was added dropwise. The reaction was allowed to warm to rt and stirred for 17 h. Water was added and the reaction was extracted with toluene. The organic layer was washed with water and dried over sodium sulfate. Solvent was removed under vacuum and the residue was dissolved in toluene, and quickly passed through a plug of silica gel pretreated with triethyl amine. Solvent was removed and the residue dried under vacuum to afford 2.65 g of the bis(trimethyltin) monomer. 1H NMR (CDCl3, 200 MHz): 6.97 (m, 2H), 1.84 (m, 4H), 1.20 (m, 16H), 0.88 (m, 6H), 0.42 (m, 18H).
##STR00035##
4,4-Dihexyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (2.2 g, 0.0065 mol) was dissolved in dry THF (20 mL). The solution was cooled to −78° C. BuLi (7.62, 2.5 M in hexanes, 0.019 mol) was then added to the solution. The reaction mixture was allowed to warm to room temperature and was stirred for 5 hours. The mixture was then cooled again to −78° C. and Bu3SnCl (7.44g, 0.0229 mol) was added. The reaction mixture was allowed to warm to room temperature and was stirred for another 48 hours. Water was then added and the mixture was extracted with dihicholomethane. Organic layer was collected, dried over anhydrous Na2SO4, and concentrated. The residue thus obtained was dissolved in hexane and quickly passed through a plug of silica gel pretreated with triethylamine. The solvent was removed and the residue was dried under vacuum to afford bis-(tributylstannyl)-4,4-dihexyl-cyclopenta[2,1-b:3,4-b′] dithiophene (5.7 g).
##STR00036##
Bis-(tributylstannyl)-4,4-dihexyl-cyclopenta[2,1-b:3,4-b′]dithiophene (0.775 g, 0.000816 mol) and 4,7-dibromo-2,1,3-benzothiadiazole (0.24 g, 0.000816 mol) were first dissolved in toluene. After the reaction was purged with nitrogen, palladium tretakistriphenylphosphine (15 mg, 0.0065 mmol) was added. The reaction mixture was heated at 100° C. for 24 hour. After the solvent was removed, the residue was washed with acetone and extracted in a Soxlet extractor for 8 hours to afford the product as an insoluble blue solid.
##STR00037##
4H-Cyclopenta[2,1-b;3,4-b′]dithiophene (1.5 g, 0.00843 mol) was dissolved in DMSO (50 mL). After the solution was purged with nitrogen, and grounded KOH (1.89 g, 0.0337 mol), sodium iodide (50 mg), and 2-ethylhexyl bromide (3.25 g, 0.0169 mol) were sequentially added. The reaction mixture was stirred overnight under nitrogen (c.a. 16 hours). Water was added and the reaction was extracted with t-butylmethyl ether. The organic layer was collected, dried over magnesium sulfate, and concentrated. The residue was purified by chromatography using hexanes as eluent. Fractions containing pure 4,4-Bis-(2-ethyl-hexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene product were combined and concentrated. The product was obtained as a colorless oil after drying under vacuum. Yield: 2.68 g (79%). 1H NMR (CDCl3, 250 MHz): 7.13 (m, 2H), 6.94 (m, 2H), 1.88 (m, 4H), 0.94 (m, 16H), 0.78 (t, 6.4 Hz, 6H), 0.61 (t, 7.3 Hz, 6H).
##STR00038##
Starting material 4,4-Bis-(2-ethyl-hexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (1.5 g, 0.00372 mol) was dissolved in dry THF (20 mL). After the solution was cooled to −78° C., butyl lithium (5.21 mL, 0.0130 mol) was added dropwise. The reaction mixture was stirred at this temperature for 1 hour. It was then warmed to room temperature and stirred for another 3 hours. The mixture was again cooled to −78° C. and trimethyltin chloride (1 M in hexane, 15.6 mL, 15.6 mmol) was added dropwise. The reaction mixture was allowed to warm to room temperature and stirred overnight (c.a. 16 hours).
Water was added and the reaction was extracted with toluene. The organic layer was washed with water, dried over sodium sulfate, and concentrated. The residue was dissolved in toluene, and quickly passed through a small plug of silica gel pretreated with triethylamine. The solvent was removed and the residue was dried under vacuum. 1.25 g of the product was obtained. 1H NMR (CDCl3, 250 MHz): 6.96 (m, 2H), 1.85 (m, 4H), 1.29 (m, 2H), 0.92 (m, 16H), 0.78 (t, 6.8 Hz, 6H), 0.61 (t, 7.3 Hz, 6H), 0.38 (m, 18H).
##STR00039##
Bis-(trimethylstannyl)-4,4-di(2-ethylhexyl)-cyclopenta[2,1-b:3,4-b′]dithiophene (0.686 g, 0.000943 mol) and 4,7-dibromo-2,1,3-benzothiadiazole (0.269 g, 0.000915 mol) were dissolved in toluene (20 mL). After the reaction was purged with nitrogen, tris(dibenzylideneacetone)dipalladium(0) (25.1 mg, 0.0275 mmol) and triphenylphosphine (57.6 mg, 0.220 mmol) were added. The reaction was further purged with nitrogen for 10 minutes and heated to 120° C. under nitrogen for 24 hours. The solvent was removed under vacuum and the residue was dissolved in chloroform. After the mixture was poured into methanol (500 mL), the blue precipitate thus obtained was collected by filtration, washed with methanol, and dried. The precipitate was dissolved in chloroform (30 mL) under heating, and filtered through a 0.45 μm membrane. The solution was loaded on to recycling HPLC (2H+2.5H column on a Dychrome recycling HPLC, 5 cycles for each injection), in 3 mL portions for purification. Higher-molecular-weight fractions were combined to give 120 mg pure polymer (Mn=35 kDa).
##STR00040##
4,4-Dihexyl-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (0.0863 g, 0.000128 mol),4,4-bis-(2-ethyl-hexyl)-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene (0.187 g, 0.000257 mol), and 4,7-Dibromo-benzo[1,2,5]thiadiazole (0.111 g, 0.000378 g) were dissolved in toluene (15 mL) and the solution was degassed and purged with N2. Tris(dibenzylideneacetone)dipalladium(0) (6.78 mg, 0.0074 mmol) and triphenylphosphine (15.5 mg, 0.0 593 mmol) were then added. The reaction was purged again with nitrogen for 30 minutes and heated at 120° C. under nitrogen. The solvent was then removed under vacuum. The residue was dissolved in chloroform and the solution was added into methanol. The precipitates were collected and extracted with hexane for 24 hours and then extracted with chloroform for 8 hours. The resultant blue solution was concentrated and added to methanol. The precipitates were collected to afford a first fraction of the polymer (70 mg). The remaining materials on the thimble was further extracted with chloroform for 20 hours. 20 mg additional polymer was collected.
##STR00041##
100 mL oven dried Schlenk flask was charged with 1.097 g (2.72 mmol) of 4H-4,4-bis(2′-ethylhexyl)cyclopenta[2,1-b:3,4-b′]dithiophene. The flask was evacuated and purged with argon three times. To this flask was then added 20 mL of dry, distilled THF. The resulting solution was cooled to −78° C. and 4.35 mL (10.88 mmol, 4 equv.) of 2.5M BuLi was added dropwise. The reaction was stirred for 1 hout at −78° C. and then warmed to room temperature and stirred for an additional 3 hours. The solution was cooled again to −78° C. and 2.77 mL (13.6 mmol, 5 equiv.) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added in one portion via syringe. The reaction was stirred at −78° C. for 1 hour and then allowed to warm to room temperature overnight. The solution was poured into water and extracted with 4×150 mL of methyl tert-butyl ether. The organic layers were combined and washed with 2×150 mL of brine, dried with anhydrous MgSO4, and filtered. The solvent was removed under vacuum to yield and orange oil, which was purified by column chromatography (5% EtOAc in hexanes) to yield a colorless, viscous oil, 1.34 g (75% yield).
##STR00042##
A 50 mL Schlenk flask was charged with 0.309 g (0.472 mmol) of 4H-4,4-bis(2′-ethylhexyl)cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-bis(pinacolborate) ester prepared in Example 9, 0.367 g (0.510 mmol) of 5,5′-dibromo-3″,4″-dihexyl-a-pentathiophene (its synthesis was described in WO 2005/092947, which is incorporated herein by reference) 0.0013 g (0.00185 mmol) of PdCl2(PPh3)2, and 0.057 g (0.142 mmol) of trioctylmethylammonium chloride (Aliquot 336, Aldrich, St. Louis, MO). The flask was fitted with a reflux condenser and the flask was evacuated and refilled with nitrogen three times. The solids were dissolved in 6 mL of toluene and then 0.88 mL of 2M Na2CO3 were added via syringe. The reaction was then heated to 95° C. with stirring for 5 hours. Phenylboronic acid (0.031 g, 0.250 mmol) and 0.0016 g (0.00228 mmol) of PdCl2(PPh3)2 were dissolved in 1 mL of THF and added to the reaction mixture, and stirring was continued for 16 h at 95° C. The reaction mixture was diluted with toluene (50 mL) and the organic layer was separated and washed with warm water (3×50 mL). The solution was then treated with an aqueous solution of diethyldithiocarbamic acid sodium salt trihydrate (7.5%, DDC, 5 mL) and heated at 80° C. overnight. The aqueous layer was separated and discarded and the organic layer was washed with warm water (3×50 mL) and the polymer precipitated into methanol (500 mL). The polymer was collected by filtration, washed with methanol (50 mL) and redissolved in hot toluene (200 mL). The hot polymer solution was passed through a tightly packed column of celite (1 x 8 cm), silica get (3×8 cm), and basic alumina (3×8 cm) (previously rinsed with 200 mL of hot toluene). The polymer solution was collected and the volume concentrated to approximately 50 mL. The polymer was precipitated into methanol (500 mL), washed with methanol (100 mL), acetone (100 mL) and again with methanol (100 mL). The polymer was then dried in vacuo overnight to yield a brick red material. Yield: 0.327 g.
The polymer solar cells were fabricated by doctor-blading a blend of the polymer prepared in Example 7 (PCPDTBT) and PC61BM or PC71BM (purchased from Nano-C, Westwood, Mass.) in a 1:3 w/w ratio sandwiched between a transparent anode and an evaporated metal cathode. The transparent anode was an indium tin oxide (ITO)-covered glass substrate (Merck, Whitehouse Station, N.J.) which was coated with a ˜60 nm thick PEDOT:PSS layer (Baytron P H from H. C. Starck) applied by doctorblading. The ITO-glass-substrate was cleaned by ultrasonification subsequently in acetone, isopropyl alcohol and deionized water. The cathode, a bilayer of a thin (1 nm) LiF layer covered with 80 nm Al, was prepared by thermal evaporation. PCPDTBT and PC61BM or PC71BM were dissolved together in o-dichlorobenzene (ODCB) to give an overall 40 mg/ml solution and was stirred overnight at 60-70° C. inside a glovebox. The active layer thickness, as determined by AFM, was between 150-250 nm. Device characterization was done under AM 1.5G irradiation (100 mW/cm2) on an Oriel Xenon solar simulator with a well calibrated spectral mismatch of 0.98 jV-characteristics were recorded with a Keithley 2400. Active areas were in the range of 15 to 20 mm2. EQE was detected with a lock-in amplifier under monochromatic illumination. Calibration of the incident light was done with a monocrystalline silicon diode. Mobility measurements were done using an Agilent 4155C parameter analyzer. Absorption measurements were done inside the glovebox with an Avantes fiberoptic spectrometer or outside with a HP spectrometer.
The interaction with PCBM and the photoinduced charge transfer was investigated by PL quenching. The PL of pristine PCPDTBT versus PCPDTBT/PCBM composites was measured at liquid N2 temperatures in a cryostat, excitation was provided by an Ar laser at 488 nm.
Electrochemical experiments were carried out on dropcast polymer films at room temperature in a glovebox. The supporting electrolyte was tetrabutylammonium-hexafluorophosphate (TBAPF6, electrochemical grade, Aldrich) ˜0.1 M in acetonitrile anhydrous (Aldrich). The working electrode (WE), as well as the counter electrode (CE), was a platinum foil. A silver wire coated with AgCl was used as a reference electrode (RE). After each measurement, the RE was calibrated with ferrocene (E0=400 mV vs. NHE) and the potential axis was corrected to NHE (using −4.75 eV for NHE24,25) according to the difference of E0 (ferrocene) and the measured E1/2 (ferrocene). λmax (CHCl3) =710 nm, λband edge (CHCl3)=780 nm, band gap (CHCl3)=1.59 eV, λmax (film)=700-760 nm, λband edge (film)=855 nm, band gap (film)=1.45 eV, HOMO=−5.3 eV, −5.7 eV (electrochem), LUMO=−3.85 eV, −4.25 eV, μ+=2×10−2 cm2/Vs (TOF), 1×10−3 cm2/Vs (FET).
Other embodiments are in the claims.
Shi, Xiaobo, Zhu, Zhengguo, Gaudiana, Russell, Kingsborough, Richard, Waller, David
| Patent | Priority | Assignee | Title |
| Patent | Priority | Assignee | Title |
| 4292092, | Jun 02 1980 | Solarex Corporation | Laser processing technique for fabricating series-connected and tandem junction series-connected solar cells into a solar battery |
| 4416959, | Nov 18 1980 | Photoelectrochemical cells for conversion of solar energy to electricity | |
| 4574160, | Sep 28 1984 | The Standard Oil Company | Flexible, rollable photovoltaic cell module |
| 4639328, | Nov 25 1983 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Thienothiophene derivatives |
| 4686323, | Jun 30 1986 | The Standard Oil Company; STANDARD OIL COMPANY, THE, A CORP OF OHIO | Multiple cell, two terminal photovoltaic device employing conductively adhered cells |
| 4746618, | Aug 31 1987 | UNITED SOLAR SYSTEMS CORP | Method of continuously forming an array of photovoltaic cells electrically connected in series |
| 4913744, | Jan 13 1987 | Solar cell arrangement | |
| 4948436, | Feb 05 1988 | Siemens Aktiengesellschaft | Thin-film solar cell arrangement |
| 5071490, | Mar 18 1988 | Sharp Kabushiki Kaisha | Tandem stacked amorphous solar cell device |
| 5221363, | Feb 28 1991 | Lockheed Corporation; Lockheed Martin Corporation | Solar cell window fitting |
| 5274058, | Sep 12 1991 | Board of Regents, The University of Texas System | Low bandgap polymers rf fused bithiophenes |
| 5510438, | |||
| 5536808, | Oct 05 1994 | The Regents of the University of Michigan | Thiazole polymers and method of producing same |
| 5708130, | Jul 28 1995 | Sumitomo Chemical Company, Limited | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
| 6109330, | Oct 09 1996 | Peter Butz GmbH & Co. Verwaltungs-KG | Blind for motor-vehicle rear window |
| 6132585, | Jul 01 1992 | Canon Kabushiki Kaisha | Semiconductor element and method and apparatus for fabricating the same |
| 6188175, | Apr 18 1995 | Cambridge Display Technology Limited | Electroluminescent device |
| 6198091, | Aug 19 1998 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Stacked organic photosensitive optoelectronic devices with a mixed electrical configuration |
| 6198092, | Aug 19 1998 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Stacked organic photosensitive optoelectronic devices with an electrically parallel configuration |
| 6239355, | Oct 09 1998 | The Trustees of Columbia University in the City of New York; TRUSTEES OF COLUMBIA UNIVERSITY IN THE CITY OF NEW YORK, THE | Solid-state photoelectric device |
| 6278055, | Aug 19 1998 | PRINCETON UNIVERSITY, THE TRUSTEES OF | Stacked organic photosensitive optoelectronic devices with an electrically series configuration |
| 6297495, | Aug 19 1998 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Organic photosensitive optoelectronic devices with a top transparent electrode |
| 6333458, | Nov 26 1999 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Highly efficient multiple reflection photosensitive optoelectronic device with optical concentrator |
| 6352777, | Aug 19 1998 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Organic photosensitive optoelectronic devices with transparent electrodes |
| 6353083, | Feb 04 1999 | The Dow Chemical Company | Fluorene copolymers and devices made therefrom |
| 6399224, | Feb 29 2000 | Canon Kabushiki Kaisha | Conjugated polymers with tunable charge injection ability |
| 6440769, | Nov 26 1999 | The Trustees of Princeton University | Photovoltaic device with optical concentrator and method of making the same |
| 6451415, | Aug 19 1998 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Organic photosensitive optoelectronic device with an exciton blocking layer |
| 6464762, | Oct 15 1997 | Canon Kabushiki Kaisha | Aqueous solution for the formation of an indium oxide film by electroless deposition |
| 6580027, | Jun 11 2001 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Solar cells using fullerenes |
| 6657378, | Sep 06 2001 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Organic photovoltaic devices |
| 6772817, | Dec 11 2000 | LEVOLOR, INC | Adjustable window blind cord stopper |
| 6818260, | Jul 09 2001 | Merck Patent GmbH | Thienothiophene derivatives |
| 6830832, | Nov 09 2001 | Sumitomo Chemical Company, Limited | Polymer compound and polymer light-emitting device using the same |
| 6864333, | Dec 28 1999 | Basell Polyolefine GmbH | Process for the preparation of ethylene polymers |
| 6962766, | Mar 30 2001 | FUJIFILM Corporation | Positive photoresist composition |
| 7095044, | Nov 28 2000 | Merck Patent GmbH | Field effect transistors and materials and methods for their manufacture |
| 7105237, | Oct 01 2003 | SAMSUNG ELECTRONICS CO , LTD | Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof |
| 7196366, | Aug 05 2004 | TRUSTEES OF PRINCETON UNIVERSITY, THE | Stacked organic photosensitive devices |
| 7309833, | Jul 29 2003 | SAMSUNG ELECTRONICS CO , LTD | Photovoltaic devices comprising layer(s) of photoactive organics dissolved in high Tg polymers |
| 7368510, | Jul 08 2004 | SAMSUNG ELECTRONICS CO , LTD | Organic semiconductor copolymers containing oligothiophene and n-type heteroaromatic units |
| 7405775, | Jan 17 2003 | FANTASY SHINE LIMITED | Display employing organic material |
| 20020040728, | |||
| 20020050289, | |||
| 20020105005, | |||
| 20030008172, | |||
| 20030023029, | |||
| 20030036612, | |||
| 20030042471, | |||
| 20030102024, | |||
| 20030127967, | |||
| 20030159729, | |||
| 20030175411, | |||
| 20030188777, | |||
| 20030189402, | |||
| 20030230335, | |||
| 20040118448, | |||
| 20040187911, | |||
| 20040192871, | |||
| 20040201018, | |||
| 20040256615, | |||
| 20050022865, | |||
| 20050145972, | |||
| 20050224905, | |||
| 20060027834, | |||
| 20060076050, | |||
| 20060155106, | |||
| 20070014939, | |||
| 20070017571, | |||
| 20070020526, | |||
| 20070120045, | |||
| 20070131270, | |||
| 20070158620, | |||
| 20070181179, | |||
| 20070193621, | |||
| 20070267055, | |||
| 20080053518, | |||
| 20080087324, | |||
| 20080121281, | |||
| 20080264488, | |||
| DE10326547, | |||
| DE3121350, | |||
| DE69330835, | |||
| EP251598, | |||
| EP1065725, | |||
| EP1318553, | |||
| EP1507298, | |||
| EP1562154, | |||
| JP2001060707, | |||
| JP2002141524, | |||
| JP2003264085, | |||
| JP2003515933, | |||
| JP4192376, | |||
| JP5011841, | |||
| WO11725, | |||
| WO22682, | |||
| WO46321, | |||
| WO139276, | |||
| WO2059121, | |||
| WO2101838, | |||
| WO3065462, | |||
| WO2004042824, | |||
| WO2007011739, | |||
| WO2007022226, | |||
| WO2007076427, | |||
| WO2007121252, | |||
| WO2007133705, | |||
| WO2007145482, | |||
| WO2008000664, | |||
| WO2010008672, | |||
| WO9414199, | |||
| WO9705184, |
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